Lubricating oil



Patented Oct. 31. 1939 LUBRICATING OIL Bert H. Lincoln and Waldo L.Steiner, Ponca City, Okla., assignors, by mesne assignments, to TheLubri-Zol Development Corporation, Cleveland, Ohio, a corporation ofDelaware No Drawing.

Application February 15, 1936,

Serial No. 64,166

7 Claims.

.Our invention relates to' lubricating oils and more particularly tosuch products as new compositions of matter.

The present design of mechanical devices calls for higher pressures onrubbing surfaces. The designers are, however, limited to pressures atwhich high quality lubricating oil will break down in use and allowmetal to metal contact and seizing. The lubricant between two rubbingsurfaces is spread out in a relatively thin film, and if the lubricantdoes not have high film strength it will break down with consequentdamage to the rubbing surfaces. Conventional hydrocarbon lubricants varyin their film strength. The very highest quality ordinary lubricants,however, do not havesufficiently high film strength properties for thedesigners of mechanical devices to take advantage of the improvementswhich might be achieved with higher rubbing pressures.

The halogens and sulphur are the elements that when added to alubricating oil in certain forms impart increased film strength andoiliness to the lubricant. Ordinarily, halogen or sulphur compounds areused alone in a lubricant to give a high film strength product.

We have discovered that combinations of halogen and sulphur compounds inthe same lubricant have certain advantages in film strength and oilinessover either when used alone. This advantage is not cumulative, but isdue to the combination of the sulphur and halogen compounds. In whatmanner this combination of halogen and sulphur compounds in the samelubricant attain this advantage is not known. Our invention rests on theimproved results obtained by the combination.

We list the groups of halogen and more specifically the chlorinecompounds with examples of each group that may be used in combinationwith sulphur compounds in any suitable lubricating base oil inpracticing this invention.

Halogen containing saturated parafiin compounds with a boiling pointabove 140 C. such as hexa-chloro-ethane, chloro-propanes, chlorobutanes,chloro-pentanes and higher homologues, such as chlorinated petroleum waxof high and low melting point.

Halogen containing unsaturated paraffin compounds with boiling pointsnear 140 C. or higher, such as tetrachloro-ethylene,hexa-chloro-propylene, chloro-butylenes, chloro-pentenes, and higherhomologues, such as the unsaturated hydrocarbons resulting from thecracking or partial pyrolitic decomposition of high boiling petroleumhydrocarbons.

Halogen containing oxygen bearing aliphatic compounds, which may besubdivided into the following subgroups:

Halogenated mono-, di-, and tri-hydric alcohols and higher homologues.Examples of halogen 5 containing alcohols are as follows: Ethylenechloro-hydrin, glyceryl mono chloro hydrin and higher homologues. l

Halogen containing aliphatic aldehydes, such as chloral and higherhomologues as for ex- 10 ample chloro-butanal, chlor'o-pentanal, etc.

Halogen containing saturated aliphatic acids such as chloro-acetic,chloro-propionic acids, and their higher homologues, as for examplechlorolauric, chloro-myristic, chloro-palmitic, chlorostearic acids,etc.

Halogen containing unsaturated acids such as chloro-crotonic,chloro-acrylic, and higher homologues such as chloro-oleic acid, etc.

Halogen containing esters of saturated and unsaturated fatty acids suchas methyl-chloro propionate, ethyl chloro-laurate,methyl-chlorostearate, and higher homologues. The equivalent mono anddi-glycol esters, the mono,-di and triglycerol esters of the abovechloro-fatty acids are included within the scope of halogenatedcompounds suitable for use inour combination.

Halogen containing substituted fatty acids and their esters of mono-,di-, tri-, and higher polyhydric alcohols such asmethyl-chloro-ricinoleic acid and its esters, etc.

Halogen containing ketones such as chloromethyl ethyl-ketone,chloro-di-butyl-ketone, and higher homologues of mixed and straighthalogen containing ketones.

Halogen containing ethers such as di-chloroethyl ether,chloro-methyl-propyl-ether, and higher homologues of these straight andmixed ethers.

It will be noted that the acids, esters and ketones may be classified aschlorinated aliphatic compounds containing a carbonyl group.

Similarly among the halogen containing compounds of the carb-o-cyclicseries, we may place in the first group the derivatives of the straighthydrocarbons. These may be divided into several subgroups as follows:

Halogen containing benzenes such as the chloro-benzencs. Halogencontaining hydrogenated and hydrocarbon substitution products of benzenesuch as chloro-toluenes, chloroxylenes. Also chloro-mono, di tri-,phenyl ben-. zenes are included in this group.

Halogen containing derivatives of naphthalene, such as mono-alphaandbeta-chloro-naphthalene and higher chlorine derivatives. Also thehydrogenated and hydrocarbon substitution products of napthalene areincluded, as for example chloro-tetralin, chloro-decalin, chloro-methylnaphthalenes, chloro-ethyl naphthalenes, etc.

Halogen containing three-membered rings and their hydrocarbonsubstitution products, as for example chloro anthracene,chloro-phenathrene,

etc.

Halogen containing terpenes, such as pinenehydro-chloride, etc.

As with the halogen containing oxygen bearing aliphatic compounds, wemay also similarly have a large group of compounds that may beclassified under the heading of halogen containing oxygen bearing ringcompounds. This large class may be divided into a number of subgroups asfollows:

Halogen containing hydroxy-aromatic compounds, such as chloro-phenols,chloro-cresols, chloro-naphthols, and homologues.

Halogen containing aromatic aldehydes, such as chloro-benzaldehydes,etc.

Halogen containing aromatic acids and their substitution products, suchas chloro-benzoic acid, chloro-salicylic acid, etc.

Halogen containing aromatic ketones and their substitution products suchas chloro-ethyl phenyl ketone, chloro-benzophenone, etc.

Halogen containing aromatic ethers and their substitution products suchas chloro-methylphenyl ether, chloro-diphenyl ether, etc.

' Halogen containing aromatic esters such as chlor-methyl-benzoate andchlor-phenyl benzoate.

Halogen containing aromatic compounds hav-- ing oxygen in the ring suchas the chlorodiphenylene oxides.

Halogen containing condensation orpolymerization products of aromaticcompounds and chlorinated aliphatic compounds where any of theconventional condensation or polymerization agents are used to promotethe combination. For example, the compound obtained by reactingnaphthalene and chloro-paraflin wax in the presence of aluminumchloride, etc. In fact, any stable chlorine compound with a boilingpoint above 140 C. may be used in this invention in combination with asuitable sulphur containing compound.

For the sulphur compound to be suitable, it must be stable in thelubricating service in which. it is employed and have a boiling point ofover 140 C. A number of these compounds are listed as follows: Butylsulfide, butyl disulfide, amyl sulfide, amyl disulfide, amyl sulfone,benzyl sulfide, para-cresyl ethyl thio-ether, dihydroxy ethyl sulfide,diphenyl sulfide, diphenyl sulfone, di-= phenyl sulfoxide, diphenylthiocarboxide, diphenyl thio-urea, dithio-diglycol, cli-para tolyldisulfide, di-para tolyl sulfide, di-para tolyl sulfone, dipara tolylsulfoxide, ethyl dithio-oxalate, ethyl thio-cyanate, heptyl sulfide,methyl-heptyl sulfide, o-tolyl thio-urea, thio-cresols, thio-phenol,thio-acids, thio-naphthols, thio-phenyl acetal, thio-acetamides,thio-imido ethers, thio-ketones, thionic acids, thiophene. It will beobserved that the foregoing compounds are of the type which aresufliciently stable so as not to substantially react with a copper stripin the conventional copper strip test. This is anessential'characteristic when the lubricating composition containing thesame is used to lubricate alloy bearings made from sensitive metals suchas copper. These compounds are therefore of the non-corrosive type. Allof the oxygen containing derivatives and the substitution products ofthiophenes and sulfones are suitable for use in accordance with ourinvention. In fact, any oil soluble sulphur compound having a boilingpoint sufficiently high 140 C. or higher) so that it will not evaporatefrom the lubricant is suitable for use in our invention. Theoxygen-bearing organic sulphur compounds are particularly suited forcertain uses and especially when employed in conjunction with a separateorganic halogen compound and more especially when such halogen compoundis a relatively stable ring compound.

A satisfactorily colloidal suspension of the sulfur compound and halogencompound may be -used in this invention in place of the true solution ofthe compounds. A physical solution of elemental sulfur in thehalogenated compound also may be used.

Some sulfur and/or halogen compounds should not be used where they willcome into contact with water. These should be used only in lubricantswhich will not come into contact with excessive moisture during theirnormal usage,

Any one or more of the above described halogens containing compounds maybe blended with any one or more of the described sulphur compounds in asuitable oil base in practicing this invention. In general, theinvention comprises the addition of relatively small quantities of thetwo types of compounds to a lubricating oil base. From 0.02 per cent to10 per cent of the halogen compound is used with quantities varying from0.02 per cent to 10 per cent of the sulphur containing compound. Thepurpose for which the oil is to be used will largely determine the kindand the quantity of addition agents required.

A suitable oil base may be defined as a hydrocarbon lubricant of acomparatively viscous or nonviscous nature, refined or unrefined,natural or synthetic. A vegetable or animal oil base is also suitablefor usein this invention.

We are aware of the use of sulphur chloride treated oils for theimprovement of lubricants. An example of such an oil is disclosed in thepatent granted to Sommer, U. S. P. 461,513. In this patent, however, thechlorine and sulphur are in altogether different relation to each othersince they are loosely held in the same molecule. The sulphur andchlorine in our invention is always found in two different molecules.

It will be understood that certain features and sub-combinations are ofutility and'may be employed without reference to other features andsub-combinations. This is contemplated by and is within the scope of ourclaims. It is further obvious that various changes may be made indetails within the scope of our claims without departing from the spiritof our invention. It is therefore, to be understood that our inventionis not to be limited to the specific details shown and described.

Having thus described our invention, what we v claim is:

1. A lubricating oil comprising in combination, a major proportion oflubricating oil and from .02 of l'per cent to 10 per cent by weight of achlorinated aliphatic compound intimately mixed with said oil togetherwith from .02 of 1 per cent to 10 per cent by weight of an organicsulphur compound, said sulphur containing and chlorinated compoundsbeing oil soluble and having a boiling point above 140 C.

2. A lubricating oil comprising in combination, a major proportion oflubricating oil and from .02

of 1 per cent to 10 per cent by weight of a chlorinated oxygen-bearingaliphatic compound intimately mixed with said oil together with from .02of 1 per cent to 10 per cent by weight of an aliphatic sulphur compound,said sulphur containing and chlorinated compounds being oil soluble andhaving a boiling point above 140 C.

3. A lubricating oil comprising in combination, a major proportion oflubricating oil and from .02 of 1 percent to 10 per cent by weight of achlorinated aliphatic compound containing a carbonyl group intimatelymixed with said oil together with from .02 of 1 per cent to 10 per centby weight of an organic sulphur compound, said sulphur containing andchlorinated compounds being oil soluble and having a boiling point above140 C.

4. A lubricating oil comprising in combination, a major proportion oflubricating oil and from .02 of 1 per cent to 10 per cent by weight ofa. chlorinated ester intimately mixed with said oil together with from.02 of 1 per cent to 10 per cent by weight of an organic sulphurcompound, said sulphur containing and chlorinated compounds being oilsoluble and having a boiling point above 140 C.

5. A lubricating oil comprising in combination, a major proportion oflubricating oil and from .02 of 1 per cent to 10 per cent by weight ofmethyl-chloro-stearate intimately mixed with said oil together with from.02 of 1 per cent to 10 per cent by weight of an organic sulphurcompound, said sulphur containing and chlorinated compounds being oilsoluble and having a boiling point above 140 C. v

6. A lubricating oil comprising in combination, a major proportion oflubricating oil and from .02 of 1 per cent to 10 per cent by weight of achlorinated aliphatic ether intimately mixed with said oil together withfrom .02 of 1 per cent to 10 per cent by weight of an organic sulphurcompound, said sulphur containing and chlorinated compounds being oilsoluble and having a boiling point above 140 C.

7. A lubricating oil comprising in combination, a major proportion oflubricating oil and from .02 of 1 per cent to 10 per cent by weight of achlorinated aliphatic hydrocarbon intimately mixed with said oiltogether with from .02 of 1 per cent to 10 per cent by weight of anorganic sulphur compound, said sulphur containing and chlorinatedcompounds being oil soluble and having a boiling point above 140 C.

BERT H. LINCOLN. WALDO L. S'I'EINER.

